US2344289A - Composition containing a diamino diazinyl substituted-alkyl sulphide - Google Patents

Description

by the following general formula:

Patented Mar. 1 4, 1944 UNITED STATES PATENT coMrosrrIoN CONTAINING A nmzmyr. SUBSTITUTED-MIL PRIDE DIAMINO SUL- Gaetano F. DAleilo and James W. Underwood, Pittsfleld, Mass, assignors to General Electric Company, corporation or New York I A No Drawing. Application Serial No. 443,97

20 Claims.

In the above formula nrepresents an integer and is at least 1 and not more than 2, X represents a halogen atom, more particularly a chlorine, bromine, fluorine or iodine atom, and R represents a member of the class consisting 01 hydrogen and monovalent hydrocarbon and substituted hydrocarbon radicals, more particularly halo-hydrocarbon radicals.

I Illustrative examples of radicals that R in theabove formula may represent are: aliphatic (e. g., methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl, butenyl, amyl, isoamyl, hexyl, octyl; allyl, methallyl, ethallyl, crotyl, etc), including cycloaliphatic (e. g., cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc); ryl (e. g., phenyl, diphenyl or xenyl, naphthyl, etc.); aliphatic-substituted aryl (e. g., tolyl, xylyl,'ethylphenyl, propylphenyl, isopropylphenyl, allylphenyl, 2-butenylphenyl, tertiaryample, a halogen,

chemical compounds such, for instance, as those represented by the general formulas:

where n, X and R have the same meanings as given above with respect to Fomula I and R. (Formulas III and IV) represents hydrogen or an unsubstituted monovalent hydrocarbon radical, numerous examples of which have been given above. 1

Instead oi the 1,3- or meta-diazines (pyrimia dines)" represented by the above formulas, corresponding derivatives of the 1,2- or orthodiazines (pyridazines) or of the 1,4- or'para-diazines (pyrazines) may be used The diazine derivatives used in carrying the present invention into eflect are more fully described and are specifically claimed in our copending application Serial No. 443,979, filed concurrently herewith and assigned to the same assigneeas the present invention.v As pointed'out in this copending application, asuitable method of preparing such diazine derivatives comprises effecting reaction in the presence 'ofa hydrohalide acceptor, e. g., an alkali-metal hydroxide,

iodophenyl bromotolyl, etc. Preferably R in the NHR groupings of Formula I is hydrogen and R in the -COOR grouping is either hydrogen or an unsubstituted monovalent hydrocarbon radical, e., g., an. aliphaticradical such as methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, crotyl, etc. However, there 'also may b used in carrying the present invention into eflect between equimolecular proportions of a mercapto diamino [(-NHR) 2] pyrimidine and a carboxy-', carboaliphaticoxy or carboaromaticoxy-' alkyl dihalide. When a carboxy (-COOH) al- ,kyl dihalide is used as a starting reactant and the hydrohalide acceptor, e. g., by an alkali metal,

the carboxy compound deslredas a flnal'prodnot is obtained by treating this intermediate product with hydrochloric, hydrobromic, sul- 4,6-di-(anilino) phuric or other suitable organic or inorganic acid in an amount just sufficient to form the desired carboxv derivative.

Examples of diazine derivatives embraced by Formula. I and which may be employed in producing the compositions of this invention are listed below:

The diamino pyrimidyl halogeno carboaliphaticoxy-methyl sulphides, including the diamino pyrimidyl chloro carboaliphaticoxy-methyl sulphides, the diamino pyrimidyl bromo carboaliphaticoxy-methyl sulphides, th'e diamino pyrimidyl iodo carboaliphaticoxy-methyl sulphides and the diamino Dyrimidyl fiuoro carboaliphaticoxy-methyl sulphides, more particu-. larly the diamino pyrimidyl halogeno (e. g.,

- chloro, bromo, etc.) alkoxy (e'. g., methoxy-, ethoxy-, propoxy-, butoxy, etc.)-methy1 sulphides The diamino pmrimidyl halogeno carboqoxymethyl sulphides, more particularly the .diamino pyrimidyl fchloro carboaroxy-methyl sulphides, the diamino pyrimidyl bromo carboaroxy-inethyl sulphides; the diamino pyrimidyl iodo carboaroxy-methyl sulphides and the diamino pyrimidyl fluoro carboaroxymethyl sulphides I The diamino pyrimidyl halogeno (chloro, bromo,

iodo, fluoro) carboxy-methyl sulphides The diamino pyrimidyl halogeno (chloro, bromo,

iodo, fluoro) carboaliphaticoxy (e. g., carbo- I alkoxy).-ethyl sulphides The diamino pyrimidyi halogeno (chloro, bromo, iodo, fluoro) carboaroxy (e. g., carbophenoxy, carbotoloxy, etc.)--ethyl sulphides ethyl sulphides 2,6-di-(methylamino) pyrimidyl-4 bromo carbomethoxy-ethyl sulphides 2,6-diamino pyrimidyl-4 bromo carbophenoxyethyl sulphides '2.6-diaminopyrimidyl-4 chloro carbomethoxy- 4,6-diamino pyrimidyl-2 chloro carbophenoxy- 2,6 di (anilino) 5-benzyl pyrimidyl-4 beta (alpha-bromo carbophenoxy-propyl) sulphide 2,6-di-(bepzylamino) 5-cyclopentyl pyrimidyl-4 alpha-(alphachloro carbotoloxy-ethyl) sulphide a 2-toluido 6-xylidino (beta-iodo carbobenzoxy-pentyl) sulphide 4,6-di-(ethylamino) pyrimidyl-Z chloro carboxymethyl sulphide pyrimidyl-Z chloro carboxymethyl sulphide 4,6-di-(bromoanilino) pyrimidyl-2 bromo carboxy-methyl sulphide 4,6 di-(cyclohexylamino) pyrimidyl-2 chloro carboxy-methyl sulphide 4,6-diamino pyrimidyl2 alpha-(alpha-chloro carbomethoxy-methyl) sulphide 2,6-.diamlno 5-methyl pyrimidyl-4 beta-(betabromo carboethoxy-ethyl) sulphide 4,6-diamino 5-phenyl pyrimidyl-2 alpha-(betachloro carbopropoxy-ethyl) sulphide 5-tolyl pyrimidyl-4 beta- 4,6 diamino pyrimidyl-2 alpha-(alpha-chloro carbophenoxy-ethyl) sulphide 4,6-diamino pyrimidyl-2 beta-(beta-bromo carbophenoxy-ethyl) sulphide 2,6-diamino 5-propy1 pyrimidy l-i alpha-(beta I 'carbophenoxy-propyl) sulphide 4,6 di-(cyclopentylamino) 5-chloroethyl pyrimidyl 2 alpha (gamma-phenyl alpha-chloro carbonaphthoxy-propyl) vsulphide 4-ethylamino S-methyl S-amino pyrimidyl-2 beta-(betaechloro carbotoloxy-ethyl) sulphide 2-naphthylamino 5-fluorophenyl 6-amino p'yrimidyl-4 beta- (beta-isobutyl *beta-bromo carbophenoxy-ethyl) sulphide 4-cyclopentenylamino 6-chloroxylidino pyrim-v idyl-2 beta-(alpha-chloro beta-benzyl carboethoxy-propyl) sulphide 4,6-diamino fi-iodophenyl pyrimidyl-2 alpha- (beta-iodo carbopentoxy-ethyl) sulphide 4,6-diamino pyrimidyl-2 beta-(alpha-bromo carboxy-ethyl) sulphide It. will be understood, of course, by those skilled in the artthat, in those compounds listed above that are generically named, the --NHR groups and the thio group may be attached in any arrangement to the symmetrical carbon atoms of the pyrimidine nucleus: In other words, the term diamino pyrimidyl includes within its meaning both the 4,6-diamino pyrimidyl-2 and the 2,6-diamino pyrimidyl-4 (2,-i-diamino pyrimidyl-fi) compounds. i

The present invention is based on our discovery that new and valuable materials of particular utility in the plastics and coating arts can be produced by eflecting reaction between ingredients comprising essentially an, aldehyde, including polymeric aldehydes, hydroxyaldehydes and aldehyde-addition products, and a halogenated compound of the kind embraced by Formula I, numerous examples of which have been given above. These new reaction products are not. only valuable in themselves,v but find particular utility when incorporated into an "acid-curing thermosetting resin, for example, acid-curing thermosetting phenoplasts and aminoplasts. For

instance, we may adda soluble, fusible aldehydereaction product of the halogen compound to an acid-curing thermosetting resin and heat the resulting mixture. The aldehydic reaction product accelerates the conversion of the acid-curing thermosetting resin to an insoluble, infusible state. Gr, we may cause the halogen compound itself to react with the acid-curing thermosetting resin and thus accelerate the curing of the resin. Or, we may form a rapidly curing resin by effecting reaction between ingredients comprising a halogen compound of the kind embraced by Formula I, an aldehyde. including polymeric aldehydes, hydroxyaldehydes and aldehyde-addition products, and a phenol (including phenol itself, cresols, xylenols, etc.) or an amino or and pressure and have idine, 2,4,6-triureido pyrimidine, also aminotriazines, e. g., melamine; ,ammeline, ammelide,

melem, melam, melon, triureido melamine, etc., aminotriazoles, e. g., guanazole, a urea, e. g.,.

urea itself, thiourea, dicyandiamide, etc.

The resin syrups and molding compositions of this invention may be stored for long periods of time without material alteration. In marked contrast the prior acid-curing thermosetting resins, more particularly those containing direct or active curing catalysts such as inorganic acids, e. g., hydrochloric, sulphuric, phosphoric, etc., lacked time or storage stability. This ne- 1 cessitated early use of the material after incorporating the catalyst.

Further, the molding compositions of this in-- vention cure rapidly under heat or under heat molding. Hence molded articles ,of even the most, complicated designs can be made rapidly and economically. The cured compositions have good color, excellent water resistance and surface finish and, in general, meet the strength, hardness and other-requirements of the particular service application.

Inpracticing the present invention the condensation between the reactants may be carried out under acid, alkaline or neutral conditions and at normal or at elevated temperatures. Any substance or catalyst which has an alkaline or an acid nature may be used to obtain the,

,,acid, alkaline or neutral condition, for example ammonia, sodium hydroxide, calcium hydroxide,

methyl amine, diethyl amine, tributyl amine, ethanol amines, tri-isopropanol amine, etc.; mixtures of such alkaline substances; inorganic or organic acids such as hydrochloric, sulphuric;

phosphoric, arcylic, crotonic, malonic, etcJ;

mixtures of such acids; acid salts such as sodium acid sulphate, monosodium phosphate, monosodi'um phthalate, etc.; basic salts such as ammonium carbonate, potassium carbonate, sodium acetate, etc.;"or mixtures of such salts.

We may condense the components used in practicing this invention under various conditions. For example, all the components may be mixed together and thereaction caused to proceed under acid, alkaline or neutral conditions. r, we-may form an acid-curing thermosetting resin (e. g., an acid-curing partial condensation product of ingredients comprising a phenol and an aldehyde, an acid-curing partial condensation product of ingredients comprising an amidogen compound, e. g., melamine, malonic diamide, 'maieic diamide, urea,/ thiourea, etc., and aldehyde), add the hereindescribed halogen compound thereto and effect further condensation: Or, we may first partially condense the halogen corhpoundwith a molecular excess of an aldehyde under acid, alkaline or. neutral conditions, and then add thereto at least one other aldehyde-reactable organic compound, e. g., a phenol, a urea, aniline,

etc., and effect further condensation. Also we may separately partially condense a halogen compoundof the kindembraced by Formula f and a different aldehyde-reactable organic compound with an aldehyde and then mix the two products of partial condensation and efi'ect further condensation therebetween- The compo-.

nents of each reaction product may be initially condensed under acid, neutral or alkaline conditions at normal or at elevated temperature.

Still other ways may be employed in combining the componentsand in producing the ungood plastic flow during J- I 3 modified and modified condensation products of this invention, as readily will be understood by weight- Example 1 Parts Urea 30.0 Aqueous formaldehyde (approx. 37.1%

HCHO) l L 64.8 Aqueous ammonia (approx. 28% NH;) 3.0 Aqueous solution of sodium hydroxide (0.46 N) .23 4,6-diamino pyrimidyl-2 bromo carbomethoxy-ethyl sulphide 1.5

were heated together under reflux at the boiling temperature of the mass for minutes. A

molding (moldable) composition was made from the resulting resinous syrup by mixing therewith 33.5 parts alpha cellulose in flock form and 0.2

part of a mold lubricant, speciflcally zinc stearate. The wet molding compound was dried at 70 C. until sufllcient moisture had been removed to provide a material that could be molded satisfactorily. A well-cured molded piece having good water resistance. was obtained by molding a sample of the-dried and ground molding compound for 5 minutes at 135 C. under a pressure of 3,500 pounds per square inch.

- Example 2 Parts 40 Melamine 31.5.

Aqueous formaldehyde I (approx. 37.1%

HCHO) 60.0 Aqueous ammonia (approx. 28% NH3) 3.2

Aqueous solution of sodium hydroxide (0.46 N) 4,6-,-diamino pyrimidyl-2 bromo carbomethoxy-ethyl sulphide 1.5

1 All of the above ingredients with the exception of the pyrimidine derivative were heated together under reflux at the boiling temperature of the mass for 13 minutes.- The pyrimidine derivative was now added and refluxing was continued for an additional 7' minutes to cause it to partial condensation product. The resulting clear syrup was mixed with 32.4 parts alpha cellulose and 0.2part zinc stearate to form a molding compound. The wetmolding composition was dried and molded as described under Example was well-cured and had a well-knit and homoa geneous structure. It had' excellent resistance to water. The molding compound showed good 5 plastic flow during molding.-

3 Example Parts Thiourea 38.0 Aqueous formaldehyde (approx. 37. v

HCHO) 90.0- Aqueous ammonia (approx. 28%,NH3) 3.8 Aqueous solution of sodium hydroxide 4,6-diamino pyrimidy1-2 bromo carbomethoxy-ethyl sulphide a 2-5 those skilled in the art as the description of inte'rcondense with themelamine-formaldehyde '1 with the exception that a molding time of only 3 minutes was employed. The molded piece I All of the above ingredients with the exception of 1.0 part of the pyrim'idine derivative were heated together under reflux at the boiling temperature of the mass for 35 minutes. The remaining one part of the pyrimidine derivative was now added and refluxing was continued for an additional 5 minutes. The resulting resinous syrup was mixed with 48.9 parts alpha cellulose and 0.3 part zinc stearate to form a molding compound. The wet molding composition was dried and molded as described under Example 1, yielding a well-cured molded piece.

Example 4 Parts 4,6-di'amino pyrimidyl-2 bromo carpomethso 8 mixing a portion of the thermosetting resin with an equal weight of alpha cellulose and molding for 5 minutes'at 140 C. under a pressure of 9,000

pounds per square inoh.

Instead of heating the reactants under reflux as above described, the mixture may be shaken.

for a longer period, for example for 24 to 72 hours or longer at room temperature. (20-30 C.) to effect reaction between the components and to obtain a soluble, fusible reaction product.

Example 5 A phenol-formaldehyde partial condensation product was prepared by heating together the following components, with constant agitation, for 2 /2 hours at approximately 85-90 0.:

. Parts Phenol (freshly distilled) 180.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 390.0

Sodium carbonate (anhydrous) 4.4

Due to a slight exothermic reaction the tempera ture rose for a brief period to 96 C. The'resinous syrup produced in this manner is identified in the following formula as syrupy phenolic resin":

, v Parts Syrupy phenolic resin 30.0 4,6-diaminopyrimldyl-2 bromo carbomethox'y-ethyl sulphide 3.09 Glycerine 2.0

The phenolic resin, which initially was dark red in color, became lighter in color as the pyrimidine derivative lowered the pH of the solution. The reaction mixture was heated slowly under reduced pressure (55 mm. mercury) until an internal resin temperature of 60 C. was reached. The resulting molasses-like liquid resin was poured into a container-and heated therein for 48 hours at 70 C. The resin cured to an insoluble and infusible' state. The 'solidified resin was hard, smooth, homogeneous, fairly light in color and opaque. This latter characteristic was due main- 1y to the fact that the liquid casting resin had been insufficiently dehydrated. The solid resin was clear in its upper portion where the water could escape.

oxy-ethyl sulphide J Aqueous formaldehyde (approx. 37.1%

HQHO) 1 160.0

. Example 6 L Parts Urea 30.0 Aqueous formaldehyde (approx. 37.1

HCHO) 67.0 Aqueous ammonia (approx. 28% NH3)' 3.5

Aqueous solution of sodium hydroxide were heated together under reflux at the boiling temperature of the mass for 20 minutes, yielding a resinous syrup that is identified in the follow-.

ing formula as urea-formaldehyde syrup:

Parts Urea-formaldehyde syrup 102.0 Reaction product of Example 4 12.0

These components were heated together under reflux at the boiling temperature of the mass for.

' 140 C. under a pressure of. 8,000 pounds per square inch. A well-cured molded piece having a well-knit and homogeneous structure was obtained. It had good resistance to water, as shown by the fact that it absorbed only 3.27% by. weight of water when tested for its water-resistance characteristics by immersing in boiling water for 15 minutes followed by immersion in cold water for-5 minutes. L

Exam ple 7 Parts Melamine 32.0

Aqueous formaldehyde (approx. 37.1%

HCHO) 61.0 Aqueous ammonia (approx. 28% N113)"; 1.5 Aqueous solution of sodium hydroxide (0.5

Parts Melamine-formaldehyde syrup 96.0 Reaction product of Example 4 6.2

These components were heated together under reflux at the'boiling temperature of the mass for 3 minutes. A molding compound was prepared by mixing 32 parts alpha cellulose and 0.2 part zinc stearate with the resulting resinous syrup.

This compound was dried and molded as described under Example 6 with the exception that a moldmg temperature of C. and a molding pressure of 6,750 pounds per square inch were employed. A well-cured molded piece having excellent resistance to water was obtained, as evidenced by the fact that it absorbed only 0.57% by weight of water when tested for its water-resistance characteristics as described under Example ".6. The molded piece had good cohesive characteris'- tics and evenness of structure, being slightly better in these respects than the molded article of Example 6. The plasticity of the molding compound during molding was very good, being somewhat better in this respect than the molding compound of Example 6.

, 4 minutes.

Example-8 Dimethyloleurea (commercial grade containing approx. 11% by weight of water.. 60.0

V were heated together under reflux at'the boiling temperature of the mass for 20 minutes, yielding a resinous syrup that is identified in the following formula as dimethylol urea syrup:

, Parts Dimethylolurea syrup 107.0 Reaction product oi. Example 4 12.0

. Parts I were heated together an open reaction vessel for 3 minutes, at the end or which period of time separation or a"resinlls took place. The

Aqueous ammonia (approx. 28% NHs) 3.5

Aqueous solution of sodium hydroxide (0.5 N). 1.6 Water 42.0

structure nor did it have quite so good cohesive characteristics as the molded products of Examples 6 and '7. The plasticity of the molding compound during molding was approximately the B sam as that of the molding compound of Example 6.

Example 9 Parts Trimethylol melamine (crystalline) 43.0 Aqueous ammonia (approx. 28% NH3) 1.2

Aqueous solution of sodium hydroxide (0.5 N) 1.0. Water 30.4

were heated together under reflux at the boiling temperature or the mass for 5 minutes, yielding a resinous syrup that is identified in the following formula as trimethylol melamine syrup:

Parts Trimethylol melamine syrup 76.0 Reaction product of Example 4 6.2.

To the mixture of the above components was added 25 parts alpha cellulose and 0.1 part zinc stearate to form a molding compound. The wet molding composition was dried and molded as described under Example 6 with the exception that a molding time of 3 minutes was employed.

The molded article was well cured and had very good resistance to water, as shown by the fact that it absorbed only 0.26% by weight of water when tested for its water-resistance characteristics as described under Example 6. The molded piece had a well-knit and homogeneous struc-' ample 7. t

2 Example 10 Parts l-phenyl guanazole 35.0 Aqueous formaldehyde (approx.- 37.1%

HCHO) 32.4 Aqueous ammonia (approx. 28% NH3) 1.2

Aqueous solution of sodium hydroxide (0.5 0 8 N) Reaction product of Example 4 l2.0

reaction mixture was mixed with 23 parts alpha cellulose and 0.1 part zinc stearate to form a molding compound. The wet molding composition was dried and molded as described under Example 6 with the exception that a molding temperature of 135 C. was employed. The molded article was well cured and absorbed only 1.07% by weight of water when tested for its waterresistance-characterlstics as described under Ex-' ample 6. The plasticity of themolding compound during molding was somewhat better than that ofany of the preceding examples.

It will be understood, of course, by those skilled in the art that the reaction between the components may be eiiected at temperatures ranging,

for example, from room temperature to the fusion or boiling temperature of the mixedreactants or of solutions of the mixed reactants, the reaction proceeding more slowly at normal temperatures than at elevatedrtemperatures in accordance with the general law of chemical reactions. Thus, instead of efiecting reaction between the. ingredients 01 the above examples under reflux at b0iling temperature as mentioned in the individual examples, the reaction between the components may be carried out at temperatures ranging,-for example, from room temperature up to the boiling temperature of the mass using substantially longer reaction periods. It will also be understood by those skilled in the art that our invention is not limited to condense-- tion products obtained by reaction of ingredients comprising an aldehyde and the specific halogen compound named in the above illustrative examples. Thus, instead of using 4,6-.-diamino pyrimidyl-2 bromo carbomethoxy-ethyl sulphide we may use, for example, 2,6-diamino pyrimidyl-4 pyrimidyl-2 chloro carbomethoxy-ethyl'sulphide,

' 2,6-diamino pyrimidyl-4 chloro carbomethoxyethyl sulphide, other diamino pyrimidyl halogeno earboaliphaticoxyeethm (or carboxy-ethyl or carboaromaticoxy-ethyl) sulphides (e. g., a diamino pyrimidyl iodo carboalkoxy-ethyl sulphide. a diamino pyrimidyl fluoro carboalkoxy-ethyl sulphide, etc.) a diamino pyrimidyl halogeno carboaromaticoxy-ethyl sulphide (e. g., a diamino pyrimidyl chloro carbophenoxy-ethyl sulphide, a diamino pyrimidyl bromo carbophenoxy-ethyl sulphide, etc.), a diamino pyrimidyl halogeno (chloro, bromo, fluoro, iodo) carboxy-ethyl sulphide, a diamino pyrimidyl halogeno carboxy-, carboaliphaticoxyor carboaromaticoxy-methyl sulphide, or any other halogen compound (or mixture thereof) embraced by Formula I, nu-

merous specific examples oi. which have-been given hereinbeiore. 7 In producinggthesenewcondensation products the choice of the aldehyde is dependent largely upon economic considerations and upon the particular properties desired in the finished product. We prefer 'to use as the aldehydic reactant tormaldehyde, or compounds engendering formaldehyde, e. g., paraformaldehyde, hexamethylene tetramine, etc. Illustrative examples of other aldehydes that may be used are acetaldehyde, propionaldehyde, butyraldehyde, acrolein'," methacrolein, crotonaldehyde, heptaldehyde, octaldehyde, benzaldehyde, furi'ural, hydroxyaldehyd'es (e. g-., glycollic aldehyde,- glyceraldehyde, etc.) mixtures thereof, or mixtures oi. formaldehyde (or compounds engen'dering formaldehyde) with such aldehydes. Illustrative examples of aldehyde-addition products that may be employed instead of the aldehydes themselves are the monoand poly-methylol derivatives of urea, thiourea, selenourea and iminourea (numerous specific examples of which are given in DAlelio copending application Serial No. 377,524, filed February 5, 1941), monoand poly-(N-carbinol) derivatives of amides of polycarboxylic acid'sfe. g., maleic, itaconic, fumaric, adipic, malonic, succinic, citric, phthalic, etc., mono-and poly-(N-carbinol) derivatives of the aminotriazoles, of the aminotriazines, etc. Particularly good results are obtained with active methylene-containing bodies such as a methylol urea, more particularly monoand di-methylol ureas, and a methylol aminotriazine, more particularly a methylo1 melamine, including monomethylol melamine and polymethylol melamines (di-, tri-, tetra-, pentaand hexa-methylol melamines). Mixtures of aldehydes and aldehyde-addition products may be employed, e. g., mixtures of formaldehyde and methylol compounds such, for instance, as diylol melamine, etc.

The ratio of the r 'ehydic reactant to the halogen compound maybevaried over a wide range depending, for example, upon the particular propmethylcl urea, trimethylol melamine, hexametherties desired in the final-product and the particaminodiazine-aldehyde resins, urea-aldehyde resins (e. g., urea-formaldehyde resins), proteinins), aniline-aldehyde resins, resinous condensaof such aldehyde-addition products ordinarily are used, for example from 1 to 15 or 20 or more mols of such alkylol derivative for each mol of the halogen compound.

When the halogen compound of the kind-embraced by Formula I is used primarily as an intercondensable curing reactant fOr accelerating the conversion of acid-curing thermosetting resins to an insoluble, infusible state, only, a relatively small amount of the halogen compound ordinarily is required, for example an amount corresponding .to from 0.2 to 013% to 5 or 6% by weight of the resin to be cured, calculated on the basis of the dry resin. In some cases it may be desirable to use higher amounts, for instance up to 8 or 9 or more parts by weight of the halogen compound per 100 parts (net dry) ofthe acid-curing thermosetting resin. When the halogen compound of the kind embraced by FormulaI is incorpo rated into the acid-curing thermosetting resin in the form of a soluble, fusible aldehyde-reaction product thereof, then higher-amounts of such reaction-product ordinarily are used as compared with the amount employed when using the'halogen compound itself. The halogen compound or itspartial reaction product with an aldehyde may be incorporated into the acid-curing thermosetting resin either prior'to, during or after the tion products of aldehydes such as formaldehyde with polyamides as, for instance, malonic diam- ,ide, maleic diamide, fumaric diamide, itaconic diamide, etc. Other examples of amino or amido compounds (amidogen compounds) that may be condensed with aldehydes such as hereinbefore mentioned by way of illustration in forming an acid-curing thermosetting resin, more particularly an acid-curing aminoplast, are thiourea, diurea, diethylene triurea, methyl urea, acetyl urea, 'benzoylurea, phenyl thiourea, asymmetrical diethyl urea, allyl urea, 2-chloroallyl urea, ethylidene urea, guanyl urea, biguanidine, melamine, triureido melamine, ammeline, ammelide, melem,

melani, melon, triamino pyrimidines, aminotriazoles, etc. Suitable mixtures of such compounds also may be used.

Phenol itself and various substituted phenols, for example the cresols, the'xylenols, etc., may be condensed with aldehydes, e. g., formaldehyde, furfural, mixtures of formaldehyde and furfural, etc., to'form acid-curing thermosetting resins of the phenoplast type, and these thermosetting resins then can be cured to the insoluble and infusible state with the aid of the hereindescribed halogen compounds or-with the soluble, fusible aldehyde-reaction products thereof.

Thermosetting molding compositions compris-' ing a filler and an acid-curing thermosetting resin carrying a curing agent comprising a halogen compound of the kind described herein, or a soluble, fusible aldehyde-reaction product of such a halogen compound, may be molded into a variety of shapes under heat and pressure, more particularly at temperatures of the order of to 200 0., preferably from approximately to 180 C. The molding compositions show good plastic fiow during molding since the curing agent not only functions as such' but also generally serves to impart improved plastic flow to the molding composition. Molded articles of manufacture comprising the molded heat-hardened molding compositions of this invention have a good surface finish, show no evidence of bleeding the curing agent, are well cured throughout, and show no loss in any of their other useful properties due to the presence of the hereindescribed halogen compound or aldehyde reaction product thereof.

What we claim as .new and desire to secure by Letters Patent of the United States is:

1. A composition comprising an acid-curing, thermosetting resin carrying a curing agent therefor comprising a compound selected from the class consisting of (1) compounds corre- ,sponding to the general formula where n represents an integer and is at least 1 and not more than 2, X represents a halogen atom, and R represents a member of the cl ass consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals: and (2) soluble, fusible aldehyde-reaction products of the compounds of (1). s

2. A composition comprising anacid-curing, thermosetting, phenol-aldehyde resin having incorporated therein a compound corresponding to the general formula Fri R-C S-[(C-RhlX)-COR] where n represents. an integer and is at least 1 and not more than 2, X represents a halogen atom, and R represents amember of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

3. A composition comprising an acid-curing, thermosetting, amidogen-aldehyde resin having incorporated therein a compound corresponding to the general formula where n represents an'integer and is at least 1 and not more than 2, x represents a halogen atom, and R represents a member of the class consisting of hydrogen and monovalent h'ydrocarbon and halo-hydrocarbon radicals.

4. A composition of matter comprising the product of reaction of ingredients comprising an aldehyde and a compound corresponding to the general formula (RHIQl IE where n represents an integer and is at least 1 and not more than 2, X represents a halogen atom, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

5. A composition as in claim 4 wherein the aldehyde is formaldehyde.

6. A composition comprising the product of reaction of ingredients comprising a phenol, an aldehyde and a compound corresponding to the general formula R-C/ \N (RHN),' (||J -s-{(c.rn. 1x)-ooon] where n represents an integer and is at least 1 and not more than 2, X represents a halogen atom, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

7. A composition comprising the product of reaction of ingredients comprising a urea. an aidehyde and a compound corresponding to the general formula 25 where n represents an integer and is at least 1 and not-more than 2, X represents a halogen atom, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

9. A product comprising the cured resinous condensation product of claim 8.

10. A condensation product of ingredients comprising an aldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 2; and R represents an unsubstituted monovalent hydrocarbon radical.

11. A condensation product of ingredients comprising an aldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 2, and R represents an unsubstituted monovalent hydrocarbon radical.

12. A composition comprising the resinous product of reaction of ingredients comprising an aminotriazine, an aldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 2, X represents a halogen atom, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

13. A composition comprising the resinous product of reaction of (1) a partial condensation product of ingredients comprising a henol and an aldehyde, and (2) a compound corresponding to the general formula where-n represents an integer and is at'least 1 and not more than 2, X represents a halogen atom and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

- 14. A composition comprising the resinous product of reaction of (1) a partial condensation product of ingredients comprising a urea and an aldehyde; and (2) a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 2, X represents a halogen atom and R represents a member of the class consistin of hydrogen and monovalent hydrocarbon andhalo-hydrocarbon radicals.

15. A composition comprising the product of reaction of ingredients comprising an aldehyde and a diamino pyrimidyl halogeno carboaliphaticoxy-ethyl sulphide.

16. A resinous composition comprising the product of reaction of (1) a partial condensation product obtained by reaction, while adand 4,6-diamino pyrimidyl-2 bromo carbomethoxy-ethyl sulphide.

19. A composition comprising the resinous product of reaction of ingredients comprising urea, formaldehyde and 4,6-diamino pyrimidyl-' 2 bromo carbomethoxy-ethyl sulphide.

20; The method of preparing new condensation products which comprises efiecting reaction between ingredients comprising an aldehyde and a compound corresponding to the general formula c where n represents an integer and is at least 1 and not more than 2, X represents a halogen atom, and R represents a member ot the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

- GAETANO F. D'AIELIO.

JAMES W. UNDERWOOD.

CERTIFICATE OF CORRECTION. Petent No. 2 1M339. March m, 191m.

GAETANO F.- D ALELIO; ET AL.

It is hereby certified that error appears in the printed. specification of the above numbered patent requiring correction as follows: PageZQfirst' colfimn, 111:18 21, for *pyyrimidyl read. -pyrimidy l-; line 57, for "diaminqpyrimidyl read -.--diamin0- pyrimidyl--; page 3 first column line 58, for'ercylic read --&cry1icpage )4, first colxhnn, line 57, Example 5,

for "d1cminopyrimidyl' read -d.iamin0 pyrimidyl"; page 5, first column,

.line 11., .Example 8, after "water" insert a closing psrehthesis; page 8,

" second column, line 10, claim l7,' for -"halogene". read -halogeno--; and

that the said Letters Patent. should he read with'this correction therein that the same may conform to the record of the case in the Patent Office.

Signed sndsealed this 25rd da Ma A, D. 19kb,.

Leslie l'razer (Seal) Acting Commissioner. of Patents.